Refractory shape



1X; ZOTEQQ 020m OON J. E- NEELY ETAL REFRACTORY SHAPE Filed July 16, 1965 July 9, 1968 (l aanldna 4 sn'moow INVENTOR. JOSEPH E. NEELY MARSHALL L. MAY

Attorney 3,392,037 REFRACTORY SHAPE Joseph E. Neely, Los Gatos, and Marshall L. Mayberry,

San Jose, Calif., assignors to Kaiser Aluminum & Chem- 3,392,037 Patented July 9, 1968 positions consisting of approximately equal parts by weight chromite and periclase grains, for example mixtures consisting of from 40% to 60% chromite and from 40% to 60% magnesia.

ical Corporation, Oakland, Calif., a corporation of 5 The alkali metal tripolyphosphate can be any one of or Delaware an admixture with each other of tripolyphosphates of the filled y 1965, 5913 472,636 usual alkali metal such as sodium, potassium, lithium, The 9 of the term of the P t subsequent to rubidium, cesium, and including ammonium. However, the ii ig z a g fi invention has been found to be particularly effective with a] 10 sodium tripolyphosphate (Na P O and with potassium Th s inv mp concerns refractory shapes and compose tripolyphosphate (-K P O as will become evident from tions from which such shapes can be made. the examples hereinafter given. The alkali metal tripoly- 0116 Of the more Important Properties Charade?" phosphate binder has been found to have maximum effecistics of refractories, for example 'q f 'y Shapes tiveness when used in an amount of about 1.1% potaseither the unfired or fired condition, 1s their strength at iu tripolyphosphate (KTPP) or about 1.4% sodium elevated temperatures, for example at temperatures above tripolyphosphate (STPP). 1000 C. It be understood that 111 the temperature It is kncwn to make refractory gunning compositions Tegion above about 0 most refractory COIIIPOSP containing, together with a plasticizing agent, from 1% tions, in either the chemically bonded, unfired form or in to 5% by weight f Sodium tripolyphosphate as the fired condition, Show a de r a In Strength, 9 is more fully set forth in U.S. patent application SN 224,- ample as measured by a modulus of rupture te t, wlth m- 223, filed Sept. 17, 1962, abandoned in favor of Neely et creasing temperature Smce these refractory {naterlals are al. $61. No. 478,980, now US. Patent 3,278,320 granted commonly used as structural elements 111 s }P f Oct. 11, 1966. Also, it is known to use from 1% to 5% ture structures, for example steel making furnaces, t will b Weight Potassium tripolyphosphate (K together he understood that it is deslra-ble to have as hlgh a ith a l i i i t, i ki a refractory gunning strength as possible at elevated temperatures. composition, as is more fully set forth in United States It has now been discovered, according to th1s invention, patent application 415,509, filed Dec. 2, 1964, no b t at a refr y With Superior stfellgqlfit a ed doned. However, it has been discovered, according to the peratures can be made from a compos1t1on CODSIS' lIJg 65- present invention, that not only are smaller amounts of sential y as gg g Sized IIOHflCld metal Oxide alkali metal tripolyphosphate effective in producing inffaciory grain as d, fr m about 0.5% to about creased strength at elevated temperatures, e.g. 1260 C., 2.0%, b d o the total weight of the c ry n of in a shaped refractory composition but, more importantly, alkali metal tripolyphosphate (M P O where M 18 all there is an effective range of amounts of alkali metal trialkali metal). polyphosphate which is useful to provide the desired The aggregate or sized refractory grain will be sized strength at elevated temperatures. This is all the more to produce a dense or close packed structure, as is well surprising when it is noted that the strength at interknown in the art. This invention has been found parmediate temperatures, e.g. 954 C., increases uninterticularly useful with nonacid refractory metal-oxide grains ruptedly with increasing amounts of alkali metal tripolysuch as periclase, chromite, and mixtures of these with phosphate, at least up to additions as high as 4.3% by each other. The invention is particularly useful in comweight, as can be seen from the data presented in Table I.

TABLE I Bond Percent MOR (p.s.i.) Composition Aggregate 20 Type Amount 954 C. 1,260 C.

5OP1/50C ig 2.0 2 5 220 185 P1/50C 2.0

0.5 2.5 450 205 3 50P1/50C Norlig Mo 1.0

&MgSO.1.HzO 1.5 3.0 200 185 4 50P1/50C r0 1.5 3.0 3.8 2.5 310 210 0.7 3.5 205 225 1.1 3.5 340 305 1.3 3.5 555 435 1.5 3.0 500 295 2.1 3.5 550 215 4.3 2.0 1,600 0.0 4.0 420 245 1.3 4.0 440 430 1.5 4.0 005 480 1.7 4.0 570 375 2.2 4.0 740 215 1.1 3.5 505 025 1.3 4.0 845 315 1.4 4.0 550 415 1.5 4.0 665 385 0.8 3.5 445 230 1.2 3.0 015 245 1.9 3.5 1,075 1.5 2.5 570 150 0: 4 "'"40 045 "455 1.5 3.5 0 189 0.77 4.5 373 233 1.1 3.5 401 970 o. 77 3.5 1.1 3.5 505 no Pl=Periclase containing 96% MgO. P2=Periclase containing 98% MgO. P3=Periclase containing 80% MgO.

O= Chrome ore.

Norlig MG=A powdered calcium magnesium sulfonate.

VS =Volatilized silica.

Compositions 1 through 25 of Table I were made up with the indicated weight proportions of periclase and chrome ore as aggregate. The periclase (P1) used had the following typical chemical compositions: 1.1% CaO, 2.1% SiO 0.3% A1 0.4% Fe O 0.3% Cr O and 95.8% MgO, by difference. The chrome ore or chromite had the following typical chemical composition: 18.4% MgO, 0.4% CaO, 5.3% SiO 29.0% A1 0 14.5% FeO, and 32.4% Cr O All this refractory aggregate passed a 4 mesh screen and all the chromite was of the size retained on a 28 mesh screen; 63.6% of the periclase passed a 100 mesh screen. The indicated type and amount, given as a weight percent of the total composition, of binders were added to the refractory aggregate. Each composition was mixed with the amount of water indicated, which was experimentally determined to give the maximum bulk density when the composition was pressed into the shape of a refractory brick about 9" x 3 X 4 /2" at a pressure of 5 tons per square inch. For STPP this amount of water was about 4% of the total weight of the dry ingredients and for KTPP about 3.5%.

Compositions 1 through 5 are indicative of typical prior art compositions using conventional cold setting or room temperature binders. (Norlig MC is a powdered calcium magnesium sulfonate manufactured by the Marathon Division of the American Can Co.) It can be seen that the modulus of rupture of these compositions at 1260 C. is less than it is at 954 C. and is around 200 p.s.i. Compositions 6 through 11 indicate the effect of varying percentages of KTPP. It can be seen that the modulus ofrupture at 954 C. of these compositions increases with increasing amounts of KTPP up to the maximum amount added, 4.3%. However, the modulus of rupture at 1260" C. can be seen to pass through a maximum as increasing amounts of KTPP are added. This effect is graphically illustrated in the attached figure, which shows modulus of rupture at 1260 C. as a function of the amount of alkali metal tripolyphosphate added. It should be noted that in the case of compositions 6 and 7, the 1260 C. modulus of rupture is actually greater than that found at 954 C. This is to be contrasted with the general decrease in strength at higher temperatures shown by the prior art compositions (1 through 5). Furthermore, the maximum 1260 C. modulus of rupture (MOR) for the KTPP-containing compositions is seen to be about twice that obtained for prior art compositions.

Compositions 12 through 16 show the effect of different percent additions of STPP as the binder, the 1260 C. MOR going through a maximum which is more than twice the strength obtained with the prior art compositions.

Compositions 17 through 20 illustrate compositions according to this invention with a slightly different weight ratio of periclase to chrome ore in the aggregate.

Compositions 21 through 24 were made using a long chain polyphosphate as binder, the particular material used being sold by FMC Corp. under the trade name Glass H. This material is a sodium polyphosphate having an average chain length of 21 phosphorous atoms. These compositions made with Glass H indicate that the enhanced elevated temperature strength found with the tripolyphosphates is not found in all polyphosphates but is peculiar to the tripolyphosphates, which have 3 phosphorous atoms.

However, although a long chain polyphosphate such as Glass H is not effective in the practice of this invention when used as the sole bonding agent, it has been found that up to half the weight of the alkali metal tripolyphosphate can be replaced with a long chain alkali metal polyphosphate with advantageous results. Composition 25 is an example of this form of the invention. It can be seen that the modulus of rupture at 1260 C. has the high value obtained with the alkali metal tripolyphosphate binders, and that in addition the 954 C. MOR has a value obtainable only with over 2% alkali metal tripolyphosphate, an amount of tripolyphosphate which leads to severely decreased 1260 C. strength. In this aspect of the invention, in other words, the refractory composition consists essentially of nonacid metal oxide refractory grain and from 0.5% to 2.0% alkali metal polyphosphate, at least half of the weight of the polyphosphate being alkali metal tripolyphosphate, the balance being a long chain alkali metal polyphosphate.

Compositions 28 and 30 are further examples of this invention using entirely periclase as aggregate. The periclase (Pl) of composition 30 is that described above, whereas the periclase (P2) used in composition 28-had the following typical chemical composition: 1.1% Ca(), 0.4% SiO 0.1% A1 0 0.2% Fe O 0.1% Cr O and 98.1% MgO, by difference. Compositions 26, 27, and 29 are comparative compositions made with the same periclases (P1 and P2) but with prior art binders. Again, it can be seen that the compositions according to this invention have strengths (MOR) at 1260 C. vastly exceeding those of the prior art compositions. It should also be noted that composition 28 had a 1260 C. MOR exceeding that of other compositions according to this invention given in Table I. The periclase'used in composition 28 contained, as a secondary phase, dicalcium silicate. It is believed that the presence of a small amount, up to 20% by weight, of dicalcium silicate as a secondary phase greatly enhances the effectiveness of the alkali metal tripolyphosphate binders of this invention.

The compositions according to this invention'have also been found to have outstanding strength properties, in comparison with compositions made with prior art binders, when fired to very high temperatures, for example temperatures of about 1700 C. or higher. These so-called high fired refractories are characterized by the fact that, in compositions containing both periclase and chromite, there is direct crystal-to-crystal bonding between the periclase and chromite crystals. Accordingly, such high fired refractories are often referred to as directbonded refractories. The compositions given in Table II were all formed into refractory brick shapes in the manner described above and then fired at a temperature of about 1700 C. The modulus of rupture of the fired specimens was determined at the temperatures indicated. Compositions 32, 33 and 34 illustrate the use of potassium tripolyphosphate and are to be compared with composition 31, using a conventional prior art bond. It can be seen that the 1260 C. MOR of fired compositions 32 and 33 exceeds that of the prior art composition 31. However, composition 34 indicates that in the fired shape 1.5% KTPP is an excessive amount.

Compositions 37, 38 and 39 illustrate the practice of this invention with KTPP in fired compositions containing only periclase (P2, the 98% MgO periclase described above) as aggregate and are to be compared with com positions 35 and 36, having the same aggregate but a prior art conventional bond. Because of the very high MgO content of the periclase used, the high temperature strength advantages of compositions according to this invention are most evident of 1400 C. The MORs at this temperature of compositions containing KTPP greatly exceed the strengths of prior art compositions, although again maximum strengths are obtained in the fired composition when the amount of KTPP is less than 1.5

Compositions 40 and 41 were made with still a third periclase (P3) as aggregate, this periclase having a typical chemical composition as follows: 12.0% C'aO, 5.4% SiO 0.5% A1 0 0.5% Fe O 0.3% Cr O and 81.3% MgO, by difference. Again the greatly increased strength at 1260 C. of the composition according to this invention, com-pared to a similar composition with a prior art bond, is illustrated. The MOR at 1400 C. for composition 41 shows that the high strength of this composition is maintained at the higher temperature.

TABLE II Bond Percent MOB (p.s.i.) Composition Aggregate :0

Type Amount 1,260 C. 1,400 C.

31 50P1/50C Norlig MC 0. 73

Alkali metal polyphosphates can be typified by the wherein said alkali metal tripolyphosphate is sodium trigogrtililuzllalcllvl gP o f whgre Mureporessergtfs alkalil metal polyt'ihos' ilhatelandt lgngtczhlainhpolylphosphatte has an n1 anm ege or p rp se is isc osure, averagec a111 eng 0 a on p osp orous aoms. the term long chain polyphosphate is intended to mean 5. A refractory composition according to claim 4 a plglyf rphtzsphate whege n its 131 or moret. fill f igll'fiin rgfractorty ggain consistcsI fessentlifal lyy of e ac ones accor mg 0 1s mven 1on are use or o to a y weig tc romite an tom 0 to 0 constructing heat exchange checkers or regenerators for by weight periclase. glass furnaces, or in the linings of high temperature metal- 6. An unfired shaped refractory article consisting essenlurgical furnaces, e.g. for constructing open hearth furtially of non-acid grain material in size ranges to provide naces, especially the roofs of such furnaces, and 1ndeed dense packing, said gram material being at least one mem- Whfirever refrgctoigies aref usegful.t d t th ber slelected cfrombthc:1 group consisting so; chrgrite fand is an a van age 0 re rac ones accor mg 0 1s peric ase, an as on mg agent rom 0 to a 0 an invention that'they show markedly increased strengths at alkali metal tripolyphosphate, said article exhibiting a le llevated temperatu'es and that they at the same time exmodulus of rupture at 1260 C. of at least 225 pounds ibit good formed ensities. per square inch.

In the specification and claims, percentages and parts 7. A refractory article according to claim 6 wherein are by weight unless otherwise indicated. Mesh sizes resaid refractory grain is periclase and said periclase conz a r e difi eci ih 0111:1133 ngi g ri fii olf iofi tings n a rii lg a i g 15 x3 h v iierein said alkali Perry, Editor-in-Chief, Third Edition, 1950 published by metal tripolyphosphate is sodium tripolyphosphate. McGraw-Hill Book Company, at page 963. For example, 9. An article according to claim 6 wherein said alkali a size passing a 100 mesh screen corresponds to 147 mimetal tripolyphosphate is potassium tripolyphosphate. crons, and that passing 200 mesh, to Z4 microns. Analyses 0 10. A refractory composition having high strength at of mmerfzlil compoiientsgre reporltzdn usaiiall malrlmtir, elevated temperatures and consisting eslsentially of per1- expresse as simpe 0x1 es, e.g., g 1 oug e c ase gram materia containing a sma amount, up to components may actually be present in various combina- 20% dicalcium silicate and as bonding agent from 0.5% tions, e.g., as a magnesium silicate. to 2.0% of alkali metal tripolyphosphate.

Having described the invention, What is claime 11. A fired, shaped refractory article consisting essen- 1. A refractory composition having high strength at tially of non-acid grain material in size ranges to provide elevated temperatures consisting essentially of sized nondense packing, said grain material being at least one memacid metal oxide refractory grain selected from the group ber selected from the group consisting of chromite and consisting of magnesia, chromite and mixtures of magpericlase, and as bonding agent from 0.5 to 2% of an nesia and chromite with each other and, as bond, from alkali metal tripolyphosphate, said article having been about 0.5% to about 2.0%, based on the total Weight fired at a temperature of at least 1700 C. and exhibiting of the composition, of alkali metal polyphosphate, at least a modulus of rupture at 1260 C. of at least 225 pounds half of said alkali metal polyphosphate being an alkali per square inch. metal tripolyphosphate, the balance of the alkali metal References Cited polyphosphate being a long chain polyphosphate. UNITED STATES PATENTS 2. A refractory composition according to claim 1 2 077 258 4/1937 Pitt et a1 wherein said long chain polyphosphate has an average 3093496 6/1963 h' z'g chain length 0f 21 Phosphmus awms- 3I27si320 10/1966 Neeley et al. -LIII: 106-58 3. A refractory composition according to claim 1 containing about 1% alkali metal tripolyphosphate and about 60 TOBIAS E. LEVOW, Primary Examiner.

0.5% long chain polyphosphate.

4. A refractory composition according to claim 3 JAMES E. POER, Examiner. 

1. A REFRACTORY COMPOSITION HAVING HIGH STRENGTH AT ELEVATED TEMPERATURES CONSISTING OF SIZED NONACID METAL OXIDE REFRACTORY GRAIN SELECTED FROM THE GROUP CONSISTING OF MAGNESIA, CHROMITE AND MIXTURES OF MAGNESIA AND CHROMITE WITH EACH OTHER AND, AS BOND, FROM ABOUT 0.5% TO ABOUT 2.0%, BASED ON THE TOTAL WEIGHT OF THE COMPOSITION, OF ALKALI METAL POLYPHOSPHATE, AT LEAST HALF OF SAID ALKALI METAL POLYPHOSPHATE BEING AN ALKALI METAL TRIPOLYPHOPSPHATE, THE BALANCE OF THE ALKALI METAL POLYPHOSPHATE BEING A LONG CHAIN POLYPHOSPHATE. 